DE2064112A1 - Isonitrile prepn - from monosubstd alkyl or aryl formamide , triphenyl or tri-dimethylamino phosphine and tetrahalomethane - Google Patents
Isonitrile prepn - from monosubstd alkyl or aryl formamide , triphenyl or tri-dimethylamino phosphine and tetrahalomethaneInfo
- Publication number
- DE2064112A1 DE2064112A1 DE19702064112 DE2064112A DE2064112A1 DE 2064112 A1 DE2064112 A1 DE 2064112A1 DE 19702064112 DE19702064112 DE 19702064112 DE 2064112 A DE2064112 A DE 2064112A DE 2064112 A1 DE2064112 A1 DE 2064112A1
- Authority
- DE
- Germany
- Prior art keywords
- tetrahalomethane
- phosphine
- isonitrile
- monosubstd
- triphenyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Verfahren zur Herstellung von Isonitrilen Es ist bekannt, daß Isonitrile aus monosubstituierten Formamiden durch Wasserabspaltung gewonnen werden können. Als Dehydratisierungsmittel hat sich dabei nach Ugi und Meyr (Chem.Ber.93,239(1960)) Phosphoroxitrichlorid in Gegenwart von Pyridin oder Kalium-tert.-butylat bewährt. Ein Nachteil dieses Verfahrens ist darin zu sehen, daß die bevorzugt angewendeten Basen Pyridin und Kalium-tert.-butylat kostspielig sind und die Aufarbeitung des Umsetzungsgemisches umständlich ist. Process for the preparation of isonitriles It is known that isonitriles can be obtained from monosubstituted formamides by splitting off water. According to Ugi and Meyr (Chem. Ber. 93,239 (1960)) Phosphorus oxitrichloride in the presence of pyridine or potassium tert-butoxide has been proven. A disadvantage of this process can be seen in the fact that the preferably used Bases pyridine and potassium tert-butoxide are expensive and the work-up of the Implementation mixture is cumbersome.
Es wurde nun überraschend gefunden, daß bei der kombinierten Einwirkung von Triphenylphosphin oder Tris(dimethylamino)-phosphin und Tetrahalogenmethan, vorzugsweise Tetrachlorkohlenstoff, auf monosubstituierte aliphatische und aromatische Formamide, besonders in Gegenwart von Basen wie z.B. Triäthylamin, glatt und in hoher Ausbeute Isonitrile gebildet werden. Die Umsetzungverläuft gemäß der nachstehenden Gleichung R=C6H5 (cH3)2N- R'= R= Alkyl, Aryl Vorzugsweise wird die Umsetzung in polaren aprotischen Lösungsmitteln wie Methylenchlorid, Chloroform, Dichloräthan, Acetonitril oder Tetrahydrofuran bei mittleren Temperaturen zwischen 0 und 80°C, vorteilhaft zwischen 20 und 60°C, durchgeführt. Nach einer anderen bevorzugten Ausführungsform wird Triphenylphosphin bzw.It has now surprisingly been found that in the combined action of triphenylphosphine or tris (dimethylamino) phosphine and tetrahalomethane, preferably carbon tetrachloride, on monosubstituted aliphatic and aromatic formamides, especially in the presence of bases such as triethylamine, isonitriles are formed smoothly and in high yield . The conversion proceeds according to the equation below R = C6H5 (cH3) 2N- R '= R = alkyl, aryl The reaction is preferably carried out in polar aprotic solvents such as methylene chloride, chloroform, dichloroethane, acetonitrile or tetrahydrofuran at average temperatures between 0 and 80 ° C, advantageously between 20 and 60 ° C, performed. According to another preferred embodiment, triphenylphosphine or
Tris(dimethylamino)-phosphin in 20- bis 30%igem Überschuß (bezogen auf vorstehende Gleichung), angewendet, wodurch die Ausbeute an Isonitrilen erhöht wird.Tris (dimethylamino) phosphine in a 20 to 30% excess (based on to the above equation), which increases the yield of isonitriles will.
Aus dem Umsetzungsgemisch können die Nitrile nach Abdestillieren des Lösungsmittels bei schwach vermindertem Druck mit geeigneten Lösungsmitteln, z.B. Petroläther, extrahiert werden. Sie werden zur Reinigung nach Abdestillieren des Lösungsmittels fraktioniert.After distilling off the nitriles, the nitriles can be removed from the reaction mixture Solvent at slightly reduced pressure with suitable Solvents, e.g. petroleum ether. They are used for cleaning after distilling off of the solvent fractionated.
Beispiele: 1. n-Butylisonitril: 8,31 g n-Butylformamid, 15,4 g Tetrachlorkohlenstoff, 10,1 g Triäthylamih und 26,1 g Triphenyl-phosphin werden in loo ccm Methylenchlorid gelöst und 2 Stunden auf 400c erwärmt. Man destilliert das Lösungsmittel unter schwach vermindertem Druck ab und extrahiert den Rückstand mehrere Male mit Petroläther (35 bis 50°C). Nach Abdestillieren des Petroläthers wird der Rückstand fraktioniert. Kp. 119°C/76O Torr. Ausbeute 6,15 g. Examples: 1. n-butyl isonitrile: 8.31 g n-butylformamide, 15.4 g carbon tetrachloride, 10.1 g of triethylamine and 26.1 g of triphenylphosphine are dissolved in 100 cc of methylene chloride dissolved and heated to 400c for 2 hours. The solvent is distilled under weak reduced pressure and the residue extracted several times with petroleum ether (35 to 50 ° C). After the petroleum ether has been distilled off, the residue is fractionated. 119 ° C / 76O Torr. Yield 6.15g.
2. Benzylisonitril: 11,7 g Benzylformamid, 15,4 g Tetrachlorkohlenstoff lo,l g Triäthylamin und 31,6 g Triphenylphosphin werden in 80 ccm Chloroform gelöst und 2 Stunden auf 600a2 erwärmt.2. Benzyl isonitrile: 11.7 g benzyl formamide, 15.4 g carbon tetrachloride Lo, l g of triethylamine and 31.6 g of triphenylphosphine are dissolved in 80 cc of chloroform and heated to 600a2 for 2 hours.
Man destilliert das Lösungsmittel ab und extrahiert den Rückstand mehrmals mit Petroläther (60 bis 950C>. Nach Abdestillieren des Petroläthers wird der Rückstand fraktioniert. Kp.: 90 bis 920C/ 10 Torr, Ausbeute 8,3 g.The solvent is distilled off and the residue is extracted several times with petroleum ether (60 to 950C>. After distilling off the petroleum ether the residue is fractionated. B.p .: 90-920C / 10 Torr, yield 8.3 g.
3. Phenylisonitril: 1o,3 g Phenylformamid 15,4 g Tetrachlorkohlenstoff lo,l g Triäthylamin und 31,6 g Triphenylphosphin werden in loo ccm Dichlorathan gelöst und 2,5 Stunden auf 600C erwärmt. Man destilliert das Lösungsmittel ab und arbeitet das Reaktionsgemisch wie bei Beispiel 2 beschrieben auf. Kp.: 54°C/12 Torr, Ausbeute 9,5 g.3. Phenylisonitrile: 10.3 g phenylformamide 15.4 g carbon tetrachloride Lo, l g of triethylamine and 31.6 g of triphenylphosphine are dissolved in 100 cc of dichloroethane dissolved and heated to 60 ° C. for 2.5 hours. The solvent is distilled off and the reaction mixture works up as described in Example 2. B.p .: 54 ° C / 12 Torr, Yield 9.5g.
Claims (4)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19702064112 DE2064112A1 (en) | 1970-12-28 | 1970-12-28 | Isonitrile prepn - from monosubstd alkyl or aryl formamide , triphenyl or tri-dimethylamino phosphine and tetrahalomethane |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19702064112 DE2064112A1 (en) | 1970-12-28 | 1970-12-28 | Isonitrile prepn - from monosubstd alkyl or aryl formamide , triphenyl or tri-dimethylamino phosphine and tetrahalomethane |
Publications (1)
Publication Number | Publication Date |
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DE2064112A1 true DE2064112A1 (en) | 1972-07-06 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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DE19702064112 Pending DE2064112A1 (en) | 1970-12-28 | 1970-12-28 | Isonitrile prepn - from monosubstd alkyl or aryl formamide , triphenyl or tri-dimethylamino phosphine and tetrahalomethane |
Country Status (1)
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DE (1) | DE2064112A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114644577A (en) * | 2020-12-18 | 2022-06-21 | 新发药业有限公司 | Environment-friendly preparation method of substituted isonitrile compound |
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1970
- 1970-12-28 DE DE19702064112 patent/DE2064112A1/en active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114644577A (en) * | 2020-12-18 | 2022-06-21 | 新发药业有限公司 | Environment-friendly preparation method of substituted isonitrile compound |
CN114644577B (en) * | 2020-12-18 | 2023-06-27 | 新发药业有限公司 | Environment-friendly preparation method of substituted isonitrile compound |
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